EP0698046A1 - Homopolymers and copolymers of 1-vinylimidazole, method of producing them and their use - Google Patents

Homopolymers and copolymers of 1-vinylimidazole, method of producing them and their use

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Publication number
EP0698046A1
EP0698046A1 EP94916182A EP94916182A EP0698046A1 EP 0698046 A1 EP0698046 A1 EP 0698046A1 EP 94916182 A EP94916182 A EP 94916182A EP 94916182 A EP94916182 A EP 94916182A EP 0698046 A1 EP0698046 A1 EP 0698046A1
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EP
European Patent Office
Prior art keywords
vinylimidazole
water
polymerization
copolymers
vinylpyrrolidone
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Granted
Application number
EP94916182A
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German (de)
French (fr)
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EP0698046B1 (en
Inventor
Juergen Detering
Walter Denzinger
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen

Definitions

  • the invention relates to homopolymers and copolymers of 1-vinylimidazole, a process for the preparation of low molecular weight polymers of 1-vinylimidazole by radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C 1 -C -Alcohols, water or in mixtures of water and at least one C -C to alcohol and the use of the polymers in detergents.
  • the present invention has for its object to provide new substances and a technically simple process for the preparation of low-monomer, low molecular weight homopolymers of 1-vinylimidazole and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone.
  • the object is achieved according to the invention with homopolymers of 1-vinylimidazole and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone if they each contain sulfur in bound form and a K value of 10 to 40 (determined according to H. Fikentscher in 0.1 n aqueous saline solution at 25 ° C and a polymer concentration of 1 wt .-%).
  • the above-mentioned homopolymers of 1-vinylimidazole and the copolymers of 1-vinylimidazole and 1-vinylpyrrolidone are also characterized in that they are obtainable by radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C -.- to C 4 alcohols, water or in mixtures of water and at least a Ci to C 4 alcohol in the presence of polymerization regulators which contain sulfur in bound form.
  • the invention also relates to a process for the preparation of low molecular weight polymers of 1-vinylimidazole by radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C- . to C 1 -C alcohols, water or in mixtures of water and at least one C 1 -C 4 alcohol, the polymerization being carried out in the presence of polymerization regulators which contain sulfur in bound form.
  • Mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides are preferably used as polymerization regulators.
  • the homopolymers and copolymers described above are used as dye transfer inhibitors in detergents.
  • Low molecular weight homopolymers and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone are prepared by the process according to the invention.
  • the homopolymers and copolymers have K values of 10-40, preferably 13 to 30 (determined according to H. Fikentscher in 0.1 N aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 1% by weight).
  • the polymerization of the monomers usually takes place in an inert gas atmosphere, e.g. B. nitrogen, argon or helium. Good mixing of the reaction partners is generally ensured during the polymerization.
  • the polymerization is in C * . - to C -Alkohlen, water or mixtures of water and at least one C- .
  • Suitable alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and isobutanol. Of the alcohols, isopropanol is preferably used.
  • the monomers can be used in any ratio in the copolymerization.
  • the monomer mixtures used in the copolymerization preferably contain 5 to 99.9% by weight of 1-vinylimidazole and 0.1 to 95% by weight of 1-vinylpyrrolidone.
  • the polymerization temperature is preferably in the range from 50 to 100 ° C. If the polymerization is carried out at higher temperatures, e.g. B. at temperatures up to 150 ° C, it is carried out in pressure-tight sealed apparatus.
  • the monomers are polymerized by free radicals, ie to initiate homopolymerization and copolymerization, compounds are required which form free radicals under the polymerization conditions.
  • radical initiators are all the usual peroxy and azo compounds, for example peroxides, hydroperoxides and peroxy esters such as hydrogen peroxide, dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxypivalate and t-butyl peroxy-2-ethylhexanoate and azo compounds such as 2 , 2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobisisobutyronitrile, 2.2 '-Azobis (2-methylbutyronitrile) and dimethyl-2, 2'-azobis (2-methylpropionate).
  • Initiator mixtures or the known redox initiators can of course also be used.
  • the initiators are used in the usual amounts, e.g. B. in amounts of 0.3 to 6 wt .-%, based on the monomers to be polymerized. If the polymerization is carried out in water or in mixtures of water and at least one of the abovementioned alcohols as solvents, water-soluble azo initiators are preferably used.
  • the polymerization is carried out in the presence of polymerization regulators which contain sulfur in bound form.
  • polymerization regulators which contain sulfur in bound form.
  • compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides, sulfones and mercapto compounds.
  • polymerization regulators are mentioned by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethyl thioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl butyl Dimethyl sulfoxide.
  • Compounds preferably used as polymerization regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides.
  • Examples of these compounds are ethylthioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropan-1,2-diol, 1, 4-mercaptobutanol, mercaptoacetic acid,
  • 3-mercapto ⁇ ropionic acid mercapto succinic acid, thioglycerol, thioacetic acid, thiourea and alkyl mercaptans such as n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan.
  • Polymerization regulators which are particularly preferably used are mercapto alcohols and mercaptocarboxylic acids.
  • the polymerization regulators, which contain sulfur in bound form, are used in amounts of 0.1 to 15, preferably 0.5 to 10,% by weight, based on the monomers used in the polymerization. Mixtures of the invention can of course also be used in the polymerization. Polymerization regulator to be used.
  • the monomers can be polymerized by the customary process techniques, for. B. after the so-called batch polymerization, in which either 1-vinylimidazole or mixtures of 1-vinylimidazole and 1-vinylpyrrolidone, regulator and initiator are placed in a solvent and heated to the polymerization temperature. The reaction mixture is stirred at the polymerization temperature until the conversion is more than 99.9%. In this process, the initiator can optionally also be added only after the polymerization temperature has been reached.
  • the feed methods which are preferably used represent further process variants for the polymerization.
  • a solution of the polymerization regulator containing sulfur in bound form and an initiator solution are added continuously or in portions.
  • Another method is to add the initiator to the receiver below or at the polymerization temperature and to feed only the regulator or a solution of the regulator to the reaction mixture within a predetermined time after the polymerization temperature has been reached.
  • Another variant of the feed technique is that the template is heated to a temperature at which the polymerization takes place and then regulator, initiator and monomers are added in separate feeds or together.
  • water or a mixture of water, monomer and / or initiator and / or regulator is preferably used as a template.
  • a method according to the invention is particularly preferred in which the polymerization regulators containing sulfur in bound form are metered in continuously or in portions during the polymerization of the monomers.
  • the weight average molecular weight Mw of the homo- and copolymers of 1-vinylimidazole thus prepared is in the range from 2,000 to 50,000, preferably 5,000 to 40,000.
  • These polymers have K values of 10 to 40 (determined according to H. Fikentscher in 0.1 N aqueous saline solution at 25 ° C and at a polymer concentration of 1% by weight).
  • the concentration of the monomers in the aqueous medium is usually 10 to 50 and is preferably in the range of 20 to 45% by weight.
  • the solutions formed during the polymerization can be subjected to a physical or chemical deodorization after the polymerization process.
  • a chemical aftertreatment the addition of polymerization initiators or mixtures of a plurality of polymerization initiators and heating of the polymer solution are carried out, if appropriate, to temperatures which are above the polymerization temperature.
  • the process according to the invention gives polymer solutions which are low in residual monomer and which can be marketed directly.
  • Such polymer solutions are used, for example, as additives to detergents. When washing colored and white textiles, they inhibit the transfer of dye to the non-colored textiles.
  • Such detergents contain, for example, 0.1 to 10, preferably 0.2 to 3% by weight of homopolymers of 1-vinylimidazole or of copolymers of 1-vinylimidazole and 1-vinylpyrrolidone.
  • the homo- and copolymers of 1-vinylimidazole obtainable by the process according to the invention are notable for high compatibility with the usual detergent constituents and have a low residual monomer content.
  • the residual monomer content of 1-vinylimidazole is usually at most 0.02% by weight.
  • the copolymer solutions usually contain less than 0.02% by weight of 1-vinylpyrrolidone.
  • the polymers obtainable according to the invention are also distinguished by an improved color.
  • the polymers can be isolated from the aqueous polymerization medium, for example by spray drying. Other drying processes, for example evaporating the polymer solution and grinding the residue or freeze-drying, are also possible.
  • the K values given in the examples were according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932) in 0.1 N aqueous saline solution at 25 ° C. solution and a polymer concentration of 1 wt .-% certainly.
  • the percentages in the examples mean% by weight.
  • the residual monomer content of the polymers was determined by gas chromatographic analysis, the molecular weight by weight average by light scattering.
  • a mixture of 200 g of 1-vinylpyrrolidone (VP), 50 g of 1-vinyl imidazole (VI) and 600 g of water is placed in a stirrer and heated to 65 ° C. with stirring in a nitrogen atmosphere. As soon as this temperature is reached, 5 g of 2,2'-azobis (2-amidinopropane) dihydrochloride, dissolved in 30 ml of water, are added. ser, too. A solution of 5 g of mercaptoethanol in 30 ml of water is then metered in continuously over the course of 1 hour. When the metering has ended, the reaction mixture is stirred at 65 ° C.
  • the aqueous polymer solution has a solids content of 30% and contains less than 50 ppm VI and less than 50 ppm VP.
  • Example 1 is repeated with the exceptions that a mixture of 175 g of 1-vinylpyrrolidone, 75 g of 1-vinylimidazole and 600 g of water is initially introduced. A light yellow clear is obtained
  • the copolymer has a K value of 22.3 and a molecular weight of 20,000.
  • the aqueous solution has a solids content of 29% and contains less than 50 ppm VI and less than 50 ppm VP.
  • a mixture of 150 g of 1-vinylpyrrolidone, 100 g of 1-vinylimidazole and 600 g of water is placed in an apparatus which is equipped with a stirrer and is equipped with a stirrer for working under a nitrogen atmosphere and is stirred onto a mixture in a nitrogen atmosphere Temperature of 70 ° C warmed. As soon as this temperature is reached, 6 g of 2,2'-azobis (2-amidino-propane) dihydrochloride, dissolved in 35 ml of water, are added. A solution of 7.6 g of diethanol disulfide in 40 ml of water is then metered in continuously over the course of 1 hour. The reaction mixture is then stirred at 70 ° C.
  • aqueous polymer solution has a solids content of 28% and contains 110 ppm VI and 150 ppm VP.
  • Example 1 is repeated with the exceptions that a mixture of 125 g VP, 125 g VI and 600 g water is presented.
  • the regulator feed consists of a solution of 5 g mercaptoacetic acid in 30 ml water. A yellow polymer solution is obtained which is clear and has little odor.
  • the K value of the copolymer is 26.8, the molecular weight 34,000.
  • the aqueous polymer solution has a solids content of
  • a mixture of 10 g of VP, 25 10 g of VI, 1.5 g of mercaptoethanol and 65 g of water is heated to 75 ° C. with stirring and nitrogen sparging. After reaching this temperature, a mixture of 135 g of VP, 135 VI, 16.2 g of mercaptoethanol and 485 g of water is used as feed 1 and a solution of 5.7 g of 2,2'-azobis (2-amidino - 30 propane) dihydrochloride metered in 100 g of water within 3 hours. The reaction mixture is then stirred at 75 ° C.
  • Example 1 is repeated with the exception that a mixture of 75 g VP, 175 g VI and 600 g water is used as the initial charge. A yellow, low-odor viscous polymer solution with a solids content of 28.4% is obtained. The copolymer has a K value of 32.5 and a molecular weight of 39,000. The aqueous Polymer solution has a low residual monomer concentration, namely 100 ppm VI and less than 50 ppm VP.
  • a mixture of 300 g of VI and 400 g of water is heated to a temperature of 80 ° C. in a nitrogen atmosphere with stirring. After this temperature has been reached, a solution of 9 g of mercaptoethanol in 50 g of water is metered in as feed 1 over the course of 2 hours and as feed 2 a solution of 7.5 g of azobis (2-methylbutyronitrile) in 70 g of isopropanol is metered in over the course of 3 hours.
  • the reaction mixture is then stirred for 1 hour at a temperature of 80 ° C., then a solution of 1.5 g of azobis (2-methylbutyronitrile) in a little isopropanol is added and the reaction mixture is stirred for a further 3 hours at 80 ° C.
  • the isopropanol is then removed from the reaction mixture using steam distillation.
  • a yellow and low-odor polymer solution is obtained with a solids content of 40% and a low residual monomer concentration (80 ppm).
  • the homopolymer of vinylimidazole has a K value of 21.5 and a molecular weight of 23,000.
  • Example 6 of DE-A-28 14 287 a mixture of 9.4 g VI, 22.2 g VP and 120 g methanol was obtained at the boiling point of the reaction mixture while passing nitrogen through in the presence of 0.6 g Copolymerized azoisobutyronitrile as an initiator. An odor-intensive polymer solution with a solids content of 24.6% was obtained. The copolymer had a K value of 49. The polymer solution contained 650 ppm VI and 6 600 ppm VP.
  • Example 5 According to the procedure given in Example 5 of DE-A-28 14 287, a mixture of 18.8 g VI, 11.1 g VP and 120 g methanol was copolymerized with 6 g azoisobutyronitrile as initiator at the boiling point of the reaction mixture. An odor-intensive polymer solution with a solids content of 22.3% was obtained. The solution contained 1.15% unpolymerized VI and 0.62% unpolymerized VP. The K value of the copolymer was 42.6. Comparative Example 3

Abstract

The invention concerns homopolymers and copolymers of 1-vinylimidazole and a method of producing low-molecular-weight homopolymers of 1-vinylimidazole and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone by the radical-mechanism polymerization of 1-vinylimidazole or mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C1 to C4 alcohol, water or a mixture of water and at least one C1 to C4 alcohol in the presence of polymerization regulators containing bound sulphur. Obtained are solutions of low-molecular-weight polymers which are low in residual monomers. The invention also concerns the use of these polymers as dye-transfer inhibiters in washing products.

Description

Homo- und Copolymerisate von 1-Vinylimidazol, Verfahren zu ihrer Herstellung und ihre VerwendungHomopolymers and copolymers of 1-vinylimidazole, process for their preparation and their use
Beschreibungdescription
Die Erfindung betrifft Homo- und Copolymerisate von 1-Vinyl- imidazol, ein Verfahren zur Herstellung von niedrigmolekularen Polymerisaten des 1-Vinylimidazols durch radikalische Polymerisa- tion von 1-Vinylimidazol oder von Mischungen aus 1-Vinylimidazol und 1-Vinylpyrrolidon in Cι~ bis C -Alkoholen, Wasser oder in Mischungen aus Wasser und mindestens einem C-.- bis C -Alkohol und die Verwendung der Polymerisate in Waschmitteln.The invention relates to homopolymers and copolymers of 1-vinylimidazole, a process for the preparation of low molecular weight polymers of 1-vinylimidazole by radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C 1 -C -Alcohols, water or in mixtures of water and at least one C -C to alcohol and the use of the polymers in detergents.
Die Herstellung von Homopolymerisaten des 1-Vinylimidazols und von Copolymerisaten aus 1-Vinylimidazol und 1-Vinylpyrrolidon durch Polymerisieren der Monomeren in Substanz oder in Lösemit¬ teln ist bekannt- vgl. DE-A-2 814 287. Die in der Literatur be¬ schriebenen Polymerisate des 1-Vinylimidazols enthalten noch größere Mengen an nichtpolymerisiertem Vinylimidazol, so daß die Polymerisate einen sehr unangenehmen Geruch besitzen, der auch noch in hoher Verdünnung wahrnehmbar ist. Um die Polymerisate zu isolieren und zu reinigen werden sie im Anschluß an ihrer Her¬ stellung einer aufwendigen und technisch nicht praktikablen Fäl- lungsoperation unterzogen.The preparation of homopolymers of 1-vinylimidazole and of copolymers of 1-vinylimidazole and 1-vinylpyrrolidone by polymerizing the monomers in bulk or in solvents is known - cf. DE-A-2 814 287. The polymers of 1-vinylimidazole described in the literature still contain relatively large amounts of unpolymerized vinylimidazole, so that the polymers have a very unpleasant odor which can also be perceived in high dilution. In order to isolate and purify the polymers, they are subjected to a complex and technically impractical precipitation operation after their preparation.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, neue Stoffe und ein technisch einfaches Verfahren zur Herstellung von restmonomerarmen, niedrigmolekularen Homopolymerisaten des 1-Vinylimidazols und von Copolymerisaten aus 1-Vinylimidazol und 1-Vinylpyrrolidon zur Verfügung zu stellen.The present invention has for its object to provide new substances and a technically simple process for the preparation of low-monomer, low molecular weight homopolymers of 1-vinylimidazole and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone.
Die Aufgabe wird erfindungsgemäß gelöst mit Homopolymerisaten von 1-Vinylimidazol und Copolymerisaten aus 1-Vinylimidazol und 1-Vinylpyrrolidon, wenn sie jeweils Schwefel in gebundener Form enthalten und einen K-Wert von 10 bis 40 (bestimmt nach H. Fikentscher in 0,1 n wäßriger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 1 Gew.-%) haben.The object is achieved according to the invention with homopolymers of 1-vinylimidazole and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone if they each contain sulfur in bound form and a K value of 10 to 40 (determined according to H. Fikentscher in 0.1 n aqueous saline solution at 25 ° C and a polymer concentration of 1 wt .-%).
Die genannten Homopolymerisate von 1-Vinylimidazol und die Copolymerisate aus 1-Vinylimidazol und 1-Vinylpyrrolidon sind außerdem dadurch gekennzeichnet, daß sie erhältlich sind durch radikalische Polymerisation von 1-Vinylimidazol oder von Mischungen aus 1-Vinylimidazol und 1-vinylpyrrolidon in C-.- bis C4-Alkoholen, Wasser oder in Mischungen aus Wasser und mindestens einem Ci- bis C4-Alkohol in Gegenwart von Polymerisationsreglern, die Schwefel in gebundener Form enthalten.The above-mentioned homopolymers of 1-vinylimidazole and the copolymers of 1-vinylimidazole and 1-vinylpyrrolidone are also characterized in that they are obtainable by radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C -.- to C 4 alcohols, water or in mixtures of water and at least a Ci to C 4 alcohol in the presence of polymerization regulators which contain sulfur in bound form.
Gegenstand der Erfindung ist außerdem ein Verfahren zur Herstel- lung von niedrigmolekularen Polymerisaten des 1-Vinylimidazols durch radikalische Polymerisation von 1-Vinylimidazol oder von Mischungen aus 1-Vinylimidazol und 1-Vinylpyrrolidon in C-.- bis C -Alkoholen, Wasser oder in Mischungen aus Wasser und mindestens einem Ci- bis C4-Alkohol, wwobei man die Polymerisation in Gegen- wart von Polymerisationsreglern durchführt, die Schwefel in ge¬ bundener Form enthalten. Als Polymerisationsregler werden vor¬ zugsweise Mercaptoverbindungen, Dialkylsulfide, Dialkyldisulfide und/oder Diarylsulfide eingesetzt.The invention also relates to a process for the preparation of low molecular weight polymers of 1-vinylimidazole by radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C- . to C 1 -C alcohols, water or in mixtures of water and at least one C 1 -C 4 alcohol, the polymerization being carried out in the presence of polymerization regulators which contain sulfur in bound form. Mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides are preferably used as polymerization regulators.
Die oben beschriebenen Homo- und Copolymerisate werden als Farb- stoffübertragungsinhibitor in Waschmitteln verwendet.The homopolymers and copolymers described above are used as dye transfer inhibitors in detergents.
Nach dem erfindungsgemäßen Verfahren werden niedrigmolekulare Homopolymerisate und Copolymerisate von 1-Vinylimidazol und 1-Vinylpyrrolidon hergestellt. Die Homo- und Copolymerisate haben K-Werte von 10 - 40, vorzugsweise 13 bis 30 (bestimmt nach H. Fikentscher in 0,1 n wäßriger Natriumchloridlösung bei 25°C und einer Polymerkonzentration von 1 Gew.-%). Die Polymerisation der Monomeren findet üblicherweise in einer Inertgasatmosphäre statt, z. B. Stickstoff, Argon oder Helium. Während der Polymerisation wird im allgemeinen für eine gute Durchmischung der Reaktions¬ partner gesorgt. Die Polymerisation wird in C*.- bis C -Alkohlen, Wasser oder Mischungen aus Wasser und mindestens einem C-.-* bis C -Alkohl durchgeführt. Vorzugsweise verwendet man Wasser oder Mischungen aus Wasser und mindestens einem C-_- bis C4-Alkohol in beliebigem Verhältnis als Lösemittel. Als Alkohole eignen sich Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, tert.-Bu- tanol und Isobutanol. Von den Alkoholen wird vorzugsweise Iso¬ propanol eingesetzt.Low molecular weight homopolymers and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone are prepared by the process according to the invention. The homopolymers and copolymers have K values of 10-40, preferably 13 to 30 (determined according to H. Fikentscher in 0.1 N aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 1% by weight). The polymerization of the monomers usually takes place in an inert gas atmosphere, e.g. B. nitrogen, argon or helium. Good mixing of the reaction partners is generally ensured during the polymerization. The polymerization is in C * . - to C -Alkohlen, water or mixtures of water and at least one C- . - * to C -Alcohol carried out. Water or mixtures of water and at least one C 1 -C 4 alcohol in any ratio are preferably used as solvents. Suitable alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and isobutanol. Of the alcohols, isopropanol is preferably used.
Zur Herstellung von Copolymerisaten aus 1-Vinylimidazol und 1-Vinylpyrrolidon kann man die Monomeren in jedem beliebigen Verhältnis bei der Copolymerisation einsetzen. Die bei der Copolymerisation eingesetzten Monomergemische enthalten bevorzugt 5 bis 99,9 Gew.-% 1-Vinylimidazol und 0,1 bis 95 Gew.-% 1-Vinyl- pyrrolidon. Die Polymerisationstemperatur liegt vorzugsweise im Bereich von 50 bis 100°C. Sofern die Polymerisation bei höheren Temperaturen durchgeführt wird, z. B. bei Temperaturen bis zu 150°C, wird sie in druckdicht verschlossenen Apparaturen vorgenom- men. Die Monomeren werden radikalisch polymerisiert, d. h. zur Initiierung der Homo- und Copolymerisation benötigt man Verbindungen, die unter den Polymerisationsbedingungen Radikale bilden. Solche Radikale bildenden Initiatoren sind alle üblichen Peroxi- und Azoverbindungen, beispielsweise Peroxide, Hydroper¬ oxide und Peroxyester wie Wasserstoffperoxid, Dibenzoylperoxid, Di-t-butylperoxid, t-Butylhydroperoxid, t-Butylperoxypivalat und t-Butylperoxy-2-ethylhexanoat sowie Azoverbindungen wie 2,2'-Azo- bis (2-amidinopropan) dihydrochlorid, 2,2'-Azo- bis [2- (2-imidazolin-2-yl)propan]dihydrochlorid, 2,2' -Azobisiso- butyronitril, 2,2'-Azobis (2-methylbutyronitril) und Dimethyl-2, 2'-azobis (2-methylpropionat) . Man kann selbstverständ¬ lich auch Initiatormischungen oder die bekannten Redoxinitiatoren verwenden. Die Initiatoren werden in den üblichen Mengen einge- setzt, z. B. in Mengen von 0,3 bis 6 Gew.-%, bezogen auf die zu polymerisierenden Monomeren. Sofern die Polymerisation in Wasser oder in Mischungen aus Wasser und mindestens einem der obenge¬ nannten Alkohole als Lösemittel durchgeführt wird, verwendet man vorzugsweise wasserlösliche Azoinitiatoren.To prepare copolymers of 1-vinylimidazole and 1-vinylpyrrolidone, the monomers can be used in any ratio in the copolymerization. The monomer mixtures used in the copolymerization preferably contain 5 to 99.9% by weight of 1-vinylimidazole and 0.1 to 95% by weight of 1-vinylpyrrolidone. The polymerization temperature is preferably in the range from 50 to 100 ° C. If the polymerization is carried out at higher temperatures, e.g. B. at temperatures up to 150 ° C, it is carried out in pressure-tight sealed apparatus. The monomers are polymerized by free radicals, ie to initiate homopolymerization and copolymerization, compounds are required which form free radicals under the polymerization conditions. Such radical initiators are all the usual peroxy and azo compounds, for example peroxides, hydroperoxides and peroxy esters such as hydrogen peroxide, dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxypivalate and t-butyl peroxy-2-ethylhexanoate and azo compounds such as 2 , 2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobisisobutyronitrile, 2.2 '-Azobis (2-methylbutyronitrile) and dimethyl-2, 2'-azobis (2-methylpropionate). Initiator mixtures or the known redox initiators can of course also be used. The initiators are used in the usual amounts, e.g. B. in amounts of 0.3 to 6 wt .-%, based on the monomers to be polymerized. If the polymerization is carried out in water or in mixtures of water and at least one of the abovementioned alcohols as solvents, water-soluble azo initiators are preferably used.
Die Polymerisation wird erfindungsgemäß in Gegenwart von Polyme¬ risationsreglern durchgeführt, die Schwefel in gebundener Form enthalten. Verbindungen dieser Art sind beispielsweise anorgani¬ sche Hydrogensulfite, Disulfite und Dithionite oder organische Sulfide, Disulfide, Polysulfide, Sulfoxide, Sulfone und Mercapto- verbindungen. Folgende Polymerisationsregler werden beispielhaft genannt: Di-n-butylsulfid, Di-n-octylsulfid, Diphenylsulfid, Thiodiglykol, Ethylthioethanol, Diisopropyldisulfid, Di-n-butyl- disulfid, Di-n-hexyldisulfid, Diacetyldisulfid, Diethanolsulfid, Di-t-butyltrisulfid und Dimethylsulfoxid. Bevorzugt als Polyme¬ risationsregler eingesetzte Verbindungen sind Mercapto- verbindungen, Dialkylsulfide, Dialkyldisulfide und/oder Diaryl- sulfide. Beispiele für diese Verbindungen sind Ethylthioglykolat, Cystein, 2-Mercaptoethanol, 1, 3-Mercaptopropanol, 3-Mercaptopro- pan-1,2-diol, 1, 4-Mercaptobutanol, Mercaptoessigsäure,According to the invention, the polymerization is carried out in the presence of polymerization regulators which contain sulfur in bound form. Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides, sulfones and mercapto compounds. The following polymerization regulators are mentioned by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethyl thioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl butyl Dimethyl sulfoxide. Compounds preferably used as polymerization regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides. Examples of these compounds are ethylthioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropan-1,2-diol, 1, 4-mercaptobutanol, mercaptoacetic acid,
3-Mercaptoρropionsäure, Mercaptobernsteinsäure, Thioglycerin, Thioessigsäure, Thioharnstoff und Alkylmercaptane wie n-Butylmer- captan, n-Hexylmercaptan oder n-Dodecylmercaptan. Besonders be¬ vorzugt eingesetzte Polymerisationsregler sind Mercaptoalkohole und Mercaptocarbonsäuren. Die Polymerisationsregler, die Schwefel in gebundener Form enthalten, werden in Mengen von 0,1 bis 15, vorzugsweise 0,5 bis 10 Gew.-%, bezogen auf die bei der Polymeri¬ sation eingesetzten Monomeren, verwendet. Bei der Polymerisation können selbstverständlich auch Mischungen der erfindungsgemäß. einzusetzenden Polymerisationsregler angewendet werden. Die Monomeren können nach den üblichen Verfahrenstechniken poly- merisiert werden, z. B. nach der sogenannten Batch-Polymerisa- tion, bei der man entweder 1-Vinylimidazol oder Mischungen aus 1-Vinylimidazol und 1-Vinylpyrrolidon, Regler und Initiator in einem Lösemittel vorlegt und auf die Polymerisationstemperatur erwärmt. Das Reaktionsgemisch wird solange bei der Polymerisati¬ onstemperatur gerührt, bis die Umsetzung mehr als 99,9 % beträgt. Die Zugabe des Initiators kann bei diesem Verfahren gegebenen¬ falls auch erst nach Erreichen der Polymerisationstemperatur er- folgen.3-mercapto ρropionic acid, mercapto succinic acid, thioglycerol, thioacetic acid, thiourea and alkyl mercaptans such as n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan. Polymerization regulators which are particularly preferably used are mercapto alcohols and mercaptocarboxylic acids. The polymerization regulators, which contain sulfur in bound form, are used in amounts of 0.1 to 15, preferably 0.5 to 10,% by weight, based on the monomers used in the polymerization. Mixtures of the invention can of course also be used in the polymerization. Polymerization regulator to be used. The monomers can be polymerized by the customary process techniques, for. B. after the so-called batch polymerization, in which either 1-vinylimidazole or mixtures of 1-vinylimidazole and 1-vinylpyrrolidone, regulator and initiator are placed in a solvent and heated to the polymerization temperature. The reaction mixture is stirred at the polymerization temperature until the conversion is more than 99.9%. In this process, the initiator can optionally also be added only after the polymerization temperature has been reached.
Weitere Verfahrensvarianten zur Polymerisation stellen die Zu¬ laufmethoden dar, die bevorzugt angewandt werden. Bei diesen Verfahrensvarianten wird zu einem Gemisch aus Vinylimidazol oder einer Mischung aus Vinylimidazol und Vinylpyrrolidon und einem Lösemittel bei der Polymerisationstemperatur innerhalb einer be¬ stimmten Zeit eine Lösung des Schwefel in gebundener Form enthal¬ tenen Polymerisationsreglers und eine Initiatorlösung kontinuier¬ lich oder portionsweise zugegeben. Es ist jedoch auch möglich, eine Mischung aus Regler und Initiator der auf Polymerisations¬ temperatur erwärmten Vorlage zuzudosieren. Eine andere Methode besteht darin, den Initiator unterhalb oder bei der Polymerisati¬ onstemperatur in die Vorlage zu geben und nur den Regler oder eine Lösung des Reglers nach Erreichen der Polymerisationstempe- ratur innerhalb eines vorgegebenen Zeitraums dem Reaktionsgemisch zuzuführen. Eine weitere Variante der Zulauftechnik besteht darin, daß man die Vorlage auf eine Temperatur erwärmt, bei der die Polymerisation abläuft und dann Regler, Initiator und Monomere in getrennten Zuläufen oder gemeinsam zugibt. Bei dieser Technik dient vorzugsweise Wasser oder ein Gemisch aus Wasser, Monomer und/oder Initiator und/oder Regler als Vorlage. Besonders bevorzugt ist erfindungsgemäß eine Verfahrensweise, bei der die Schwefel in gebundener Form enthaltenden Polymerisationsregler während der Polymerisation der Monomeren kontinuierlich oder por- tionsweise zudosiert werden.The feed methods which are preferably used represent further process variants for the polymerization. In these process variants, to a mixture of vinylimidazole or a mixture of vinylimidazole and vinylpyrrolidone and a solvent at the polymerization temperature, a solution of the polymerization regulator containing sulfur in bound form and an initiator solution are added continuously or in portions. However, it is also possible to meter a mixture of regulator and initiator into the receiver heated to the polymerization temperature. Another method is to add the initiator to the receiver below or at the polymerization temperature and to feed only the regulator or a solution of the regulator to the reaction mixture within a predetermined time after the polymerization temperature has been reached. Another variant of the feed technique is that the template is heated to a temperature at which the polymerization takes place and then regulator, initiator and monomers are added in separate feeds or together. In this technique, water or a mixture of water, monomer and / or initiator and / or regulator is preferably used as a template. A method according to the invention is particularly preferred in which the polymerization regulators containing sulfur in bound form are metered in continuously or in portions during the polymerization of the monomers.
Das Molekulargewicht nach dem Gewichtsmittel Mw der so hergestell¬ ten Homo- und Copolymerisate des 1-Vinylimidazols liegt in dem dem Bereich von 2 000 bis 50 000, vorzugsweise 5 000 bis 40 000. Diese Polymerisate haben K-Werte von 10 bis 40 (bestimmt nach H. Fikentscher in 0,1 n wäßriger Kochsalzlösung bei 25°C und bei einer Polymerkonzentration von 1 Gew.-%). Die Konzentration der Monomeren in dem wäßrigen Medium beträgt üblicherweise 10 bis 50 und liegt vorzugsweise in dem Bereich von 20 bis 45 Gew.-%. Die bei der Polymerisation entstehenden Lösungen können im Anschluß an den Polymerisationsprozeß einer physikalischen oder chemischen Desodorierung unterworfen werden. Darunter versteht man u.a. eine Nachbehandlung der Polymerlösung mittels Wasserdampfdestillation oder Strippen mit Stickstoff, wobei mit Wasserdampf flüchtige Verunreinigungen aus der Lösung entfernt werden. Bei einer chemi¬ schen Nachbehandlung erfolgt der Zusatz von Polymerisationsini- tiatoren oder Mischungen mehrerer Polymerisationsinitiatoren und Erhitzen der Polymerlösung gegebenenfalls auf Temperaturen, die oberhalb der Polymerisationstemperatur liegen.The weight average molecular weight Mw of the homo- and copolymers of 1-vinylimidazole thus prepared is in the range from 2,000 to 50,000, preferably 5,000 to 40,000. These polymers have K values of 10 to 40 (determined according to H. Fikentscher in 0.1 N aqueous saline solution at 25 ° C and at a polymer concentration of 1% by weight). The concentration of the monomers in the aqueous medium is usually 10 to 50 and is preferably in the range of 20 to 45% by weight. The solutions formed during the polymerization can be subjected to a physical or chemical deodorization after the polymerization process. This means, among other things, one Aftertreatment of the polymer solution by means of steam distillation or stripping with nitrogen, volatile impurities being removed from the solution using steam. In the case of a chemical aftertreatment, the addition of polymerization initiators or mixtures of a plurality of polymerization initiators and heating of the polymer solution are carried out, if appropriate, to temperatures which are above the polymerization temperature.
Nach dem erfindungsgemäßen Verfahren erhält man restmonomerarme Polymerlösungen, die direkt in den Handel gebracht werden können. Solche Polymerlösungen werden beispielsweise als Zusatz zu Wasch¬ mitteln verwendet. Sie bewirken beim Waschen von gefärbten und weißen Textilien eine Inhibierung der Farbstoffübertragung auf die nichtgefärbten Textilien. Solche Waschmittel enthalten bei- spielsweise 0,1 bis 10, vorzugsweise 0,2 bis 3 Gew.-% an Homo¬ polymerisaten des 1-Vinylimidazols oder an Copolymerisaten aus 1-Vinylimidazol und 1-Vinylpyrrolidon. Die nach dem erfindungs¬ gemäßen Verfahren erhältlichen Homo- und Copolymerisate von 1-Vinylimidazol zeichnen sich durch eine hohe Verträglichkeit mit den üblichen Waschmittelbestandteilen aus und besitzen einen nie¬ drigen Restmonomergehalt . Der Restmonomergehalt an 1-Vinyl- imidazol liegt üblicherweise bei höchstens 0,02 Gew.-%. Die Copo- lymerlösungen enthalten üblicherweise weniger als 0,02 Gew.-% 1-Vinylpyrrolidon. Gegenüber den bisher bekannten Polymerlösungen zeichnen sich die erfindungsgemäß erhältlichen Polymeren außerdem durch eine verbesserte Farbe aus. Die Polymeren können aus dem wäßrigen Polymerisationsmedium beispielsweise durch Sprüh¬ trocknung isoliert werden. Andere Trocknungsverfahren, beispiels¬ weise Eindampfen der Polymerlösung und Mahlen des Rückstandes oder Gefriertrocknen sind ebenfalls möglich.The process according to the invention gives polymer solutions which are low in residual monomer and which can be marketed directly. Such polymer solutions are used, for example, as additives to detergents. When washing colored and white textiles, they inhibit the transfer of dye to the non-colored textiles. Such detergents contain, for example, 0.1 to 10, preferably 0.2 to 3% by weight of homopolymers of 1-vinylimidazole or of copolymers of 1-vinylimidazole and 1-vinylpyrrolidone. The homo- and copolymers of 1-vinylimidazole obtainable by the process according to the invention are notable for high compatibility with the usual detergent constituents and have a low residual monomer content. The residual monomer content of 1-vinylimidazole is usually at most 0.02% by weight. The copolymer solutions usually contain less than 0.02% by weight of 1-vinylpyrrolidone. Compared to the previously known polymer solutions, the polymers obtainable according to the invention are also distinguished by an improved color. The polymers can be isolated from the aqueous polymerization medium, for example by spray drying. Other drying processes, for example evaporating the polymer solution and grinding the residue or freeze-drying, are also possible.
Die in den Beispielen angegebenen K-Werte wurden nach H. Fikentscher, Cellulose-Chemie, Band 13, 58 bis 64 und 71 bis 74 (1932) in 0,1 n wäßriger Kochsalzlösung bei 25°C-Lösung und einer Polymerkonzentration von 1 Gew.-% bestimmt. Die Prozent¬ angaben in den Beispielen bedeuten Gew.-%. Der Restmonomergehalt der Polymerisate wurde durch gaschromatographische Analyse, das Molekulargewicht nach dem Gewichtsmittel durch Lichtstreuung be¬ stimmt.The K values given in the examples were according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932) in 0.1 N aqueous saline solution at 25 ° C. solution and a polymer concentration of 1 wt .-% certainly. The percentages in the examples mean% by weight. The residual monomer content of the polymers was determined by gas chromatographic analysis, the molecular weight by weight average by light scattering.
Beispiel 1example 1
Ein Gemisch aus 200 g 1-Vinylpyrrolidon (VP), 50 g 1-Vinyl¬ imidazol (VI) und 600 g Wasser wird in einer Rührapparatur vqrge- legt und unter Rühren in einer Stickstoffatmosphäre auf 65°C er¬ wärmt. Sobald diese Temperatur erreicht ist, gibt man 5 g 2,2' -Azobis (2-amidinopropan) dihydrochlorid, gelöst in 30 ml Was- ser, zu. Anschließend dosiert man innerhalb von 1 Stunde eine Lösung von 5 g Mercaptoethanol in 30 ml Wasser kontinuierlich zu. Nach beendeter Dosierung wird das Reaktionsgemisch 2 Stunden bei 65°C gerührt, dann mit 1,25 g 2,2'-Azobis (2-amidinopropan)dihydro- chlorid versetzt und weitere 3 Stunden bei 65°C gerührt. Man er¬ hält eine hellgelbe, geruchsarme, viskose Polymerlösung. Der K- Wert des Copolymers beträgt 27,4, das Molekulargewicht 28 000. Die wäßrige Polymerlösung hat einen Feststoffgehalt von 30 % und enthält weniger als 50 ppm VI und weniger als 50 ppm VP .A mixture of 200 g of 1-vinylpyrrolidone (VP), 50 g of 1-vinyl imidazole (VI) and 600 g of water is placed in a stirrer and heated to 65 ° C. with stirring in a nitrogen atmosphere. As soon as this temperature is reached, 5 g of 2,2'-azobis (2-amidinopropane) dihydrochloride, dissolved in 30 ml of water, are added. ser, too. A solution of 5 g of mercaptoethanol in 30 ml of water is then metered in continuously over the course of 1 hour. When the metering has ended, the reaction mixture is stirred at 65 ° C. for 2 hours, then 1.25 g of 2,2′-azobis (2-amidinopropane) dihydrochloride are added and the mixture is stirred at 65 ° C. for a further 3 hours. A light yellow, low-odor, viscous polymer solution is obtained. The K value of the copolymer is 27.4, the molecular weight is 28,000. The aqueous polymer solution has a solids content of 30% and contains less than 50 ppm VI and less than 50 ppm VP.
Beispiel 2Example 2
Beispiel 1 wird mit den Ausnahmen wiederholt, daß man als Vorlage eine Mischung aus 175 g 1-Vinylpyrrolidon, 75 g 1-Vinylimidazol und 600 g Wasser vorlegt. Man erhält eine hellgelbe klareExample 1 is repeated with the exceptions that a mixture of 175 g of 1-vinylpyrrolidone, 75 g of 1-vinylimidazole and 600 g of water is initially introduced. A light yellow clear is obtained
Polymerlösung ohne den typischen Geruch nach 1-Vinylimidazol. Das Copolymerisat hat einen K-Wert von 22,3 und ein Molekulargewicht von 20 000. Die wäßrige Lösung hat einen Feststoffgehalt von 29 % und enthält weniger als 50 ppm VI und weniger als 50 ppm VP.Polymer solution without the typical smell of 1-vinylimidazole. The copolymer has a K value of 22.3 and a molecular weight of 20,000. The aqueous solution has a solids content of 29% and contains less than 50 ppm VI and less than 50 ppm VP.
Beispiel 3Example 3
In einer für das Arbeiten unter einer Stickstoffatmosphäre ausge¬ rüsteten Apparatur, die mit einem Rührer versehen ist, wird ein Gemisch aus 150 g 1-Vinylpyrrolidon, 100 g 1-Vinylimidazol und 600 g Wasser vorgelegt und unter Rühren in einer Stickstoff¬ atmosphäre auf eine Temperatur von 70°C erwärmt. Sobald diese Temperatur erreicht ist, gibt man 6 g 2,2'-Azobis (2-amidino- propan)dihydrochlorid, gelöst in 35 ml Wasser, zu. Anschließend dosiert man kontinuierlich innerhalb von 1 Stunde eine Lösung von 7,6 g Diethanoldisulfid in 40 ml Wasser zu. Danach wird das Reak¬ tionsgemisch 2 Stunden bei 70°C gerührt, mit 1,5 g 2,2' -Azo¬ bis (2-amidinopropan)dihydrochlorid versetzt und weitere 4 Stunden bei 70°C gerührt. Man erhält eine gelbe, geruchsarme wäßrige Polymerlösung. Der K-Wert des Copolymeren beträgt 24,7, das Mole¬ kulargewicht 26 000. Die wäßrige Polymerlösung hat einen Fest¬ stoffgehalt von 28 % und enthält 110 ppm VI und 150 ppm VP.A mixture of 150 g of 1-vinylpyrrolidone, 100 g of 1-vinylimidazole and 600 g of water is placed in an apparatus which is equipped with a stirrer and is equipped with a stirrer for working under a nitrogen atmosphere and is stirred onto a mixture in a nitrogen atmosphere Temperature of 70 ° C warmed. As soon as this temperature is reached, 6 g of 2,2'-azobis (2-amidino-propane) dihydrochloride, dissolved in 35 ml of water, are added. A solution of 7.6 g of diethanol disulfide in 40 ml of water is then metered in continuously over the course of 1 hour. The reaction mixture is then stirred at 70 ° C. for 2 hours, 1.5 g of 2,2′-azobis (2-amidinopropane) dihydrochloride are added, and the mixture is stirred at 70 ° C. for a further 4 hours. A yellow, low-odor aqueous polymer solution is obtained. The K value of the copolymer is 24.7 and the molecular weight is 26,000. The aqueous polymer solution has a solids content of 28% and contains 110 ppm VI and 150 ppm VP.
Beispiel 4Example 4
Beispiel 1 wird mit den Ausnahmen wiederholt, daß man ein Gemisch aus 125 g VP, 125 g VI und 600 g Wasser vorlegt. Der Reglerzulauf besteht aus einer Lösung von 5 g Mercaptoessigsäure in 30 ml Was¬ ser. Man erhält eine gelbe Polymerlösung, die klar und geruchsarm ist. Der K-Wert des Copolymers beträgt 26,8, das Molekulargewicht 34 000. Die wäßrige Polymerlösung hat einen Feststoffgehalt vonExample 1 is repeated with the exceptions that a mixture of 125 g VP, 125 g VI and 600 g water is presented. The regulator feed consists of a solution of 5 g mercaptoacetic acid in 30 ml water. A yellow polymer solution is obtained which is clear and has little odor. The K value of the copolymer is 26.8, the molecular weight 34,000. The aqueous polymer solution has a solids content of
30 % und enthält weniger als 50 ppm VI und weniger als 50 ppm VP.30% and contains less than 50 ppm VI and less than 50 ppm VP.
Beispiel 5 5Example 5 5
In einer Rührapparatur werden 125 g VP, 125 g VI und 600 g Wasser vorgelegt und unter StickstoffSpülung und Rühren auf 75°C erhitzt. Sobald das Reaktionsgemisch eine Temperatur von 70°C erreicht hat, dosiert man als Zulauf 1 eine Lösung von 5 g 2,2'-Azo-125 g of VP, 125 g of VI and 600 g of water are placed in a stirring apparatus and heated to 75 ° C. with nitrogen purging and stirring. As soon as the reaction mixture has reached a temperature of 70 ° C., a solution of 5 g of 2,2'-azo-
10 bis (2-amidinopropan) dihydrochlorid in 100 ml Wasser innerhalb von 100 Minuten und als Zulauf 2 eine Lösung von 10 g Mercaptoethanol in 50 ml Wasser innerhalb von 70 Minuten. Nach Beendigung der Do¬ sierung des Initiators wird das Reaktionsgemisch 75 Minuten bei einer Temperatur von 75°C gerührt, anschließend mit 1,25 g10 bis (2-amidinopropane) dihydrochloride in 100 ml water within 100 minutes and as feed 2 a solution of 10 g mercaptoethanol in 50 ml water within 70 minutes. After the metering of the initiator has ended, the reaction mixture is stirred for 75 minutes at a temperature of 75 ° C., then with 1.25 g
15 2,2'-Azobis (2-amidinopropan)dihydrochlorid versetzt und weitere 2 Stunden bei 75°C gerührt. Die so erhaltene gelbe, klare Polymer¬ lösung mit einem Feststoffgehalt von 26,4 % ist geruchsarm und restmonomerenarm. Sie enthält weniger als 50 ppm VI und weniger als 50 ppm V . Das Copolymerisat hat einen K-Wert von 19,4 und15 2,2'-azobis (2-amidinopropane) dihydrochloride were added and the mixture was stirred at 75 ° C. for a further 2 hours. The yellow, clear polymer solution thus obtained with a solids content of 26.4% is low in odor and low in residual monomers. It contains less than 50 ppm VI and less than 50 ppm V. The copolymer has a K value of 19.4 and
20 ein Molekulargewicht von 12 000.20 a molecular weight of 12,000.
Beispiel 6Example 6
In einer Polymerisationsapparatur wird ein Gemisch aus 10 g VP, 25 10 g VI, 1,5 g Mercaptoethanol und 65 g Wasser unter Rühren und Stickstoffbegasung auf eine Temperatur von 75°C erwärmt. Nach Er¬ reichen dieser Temperatur wird als Zulauf 1 eine Mischung aus 135 g VP, 135 VI, 16,2 g Mercaptoethanol und 485 g Wasser und als Zulauf 2 eine Lösung von 5,7 g 2,2'-Azobis (2-amidino- 30 propan)dihydrochlorid in 100 g Wasser innerhalb von 3 Stunden zudosiert. Das Reaktionsgemisch wird anschließend 30 Minuten bei 75°C gerührt und danach mit einer wäßrigen Lösung von 1,5 g 2,2'-Azobis (2-amidinopropan)dihydrochlorid in 10 g Wasser inner¬ halb von 5 Minuten versetzt und 2,5 Stunden bei 75°C gerührt. Man 35 erhält eine gelbe, klare, geruchsarme Polymerlösung mit einem Feststoffgehalt von 33 %. Sie enthält weniger als 50 ppm VI und weniger als 50 ppm VP. Das Copolymerisat hat einen K-Wert von 15 und ein Molekulargewicht von 6 000.In a polymerization apparatus, a mixture of 10 g of VP, 25 10 g of VI, 1.5 g of mercaptoethanol and 65 g of water is heated to 75 ° C. with stirring and nitrogen sparging. After reaching this temperature, a mixture of 135 g of VP, 135 VI, 16.2 g of mercaptoethanol and 485 g of water is used as feed 1 and a solution of 5.7 g of 2,2'-azobis (2-amidino - 30 propane) dihydrochloride metered in 100 g of water within 3 hours. The reaction mixture is then stirred at 75 ° C. for 30 minutes and then mixed with an aqueous solution of 1.5 g of 2,2'-azobis (2-amidinopropane) dihydrochloride in 10 g of water within 5 minutes and for 2.5 hours stirred at 75 ° C. A yellow, clear, low-odor polymer solution with a solids content of 33% is obtained. It contains less than 50 ppm VI and less than 50 ppm VP. The copolymer has a K value of 15 and a molecular weight of 6,000.
40 Beispiel 740 Example 7
Beispiel 1 wird mit der Ausnahme wiederholt, daß man als Vorlage ein Gemisch aus 75 g VP, 175 g VI und 600 g Wasser verwendet. Man erhält ein gelbe, geruchsarme viskose Polymerlösung mit einem 45 Feststoffgehalt von 28,4 %. Das Copolymerisat hat einen K-Wert von 32,5 und ein Molekulargewicht von 39 000. Die wäßrige Polymerlösung hat eine niedrige Restmonomerkonzentration, und zwar 100 ppm VI und weniger als 50 ppm VP .Example 1 is repeated with the exception that a mixture of 75 g VP, 175 g VI and 600 g water is used as the initial charge. A yellow, low-odor viscous polymer solution with a solids content of 28.4% is obtained. The copolymer has a K value of 32.5 and a molecular weight of 39,000. The aqueous Polymer solution has a low residual monomer concentration, namely 100 ppm VI and less than 50 ppm VP.
Beispiel 8Example 8
In einer Polymerisationsapparatur wird ein Gemisch aus 300 g VI und 400 g Wasser in einer Stickstoffatmosphäre unter Rühren auf eine Temperatur von 80°C erhitzt. Nach Erreichen dieser Temperatur wird als Zulauf 1 eine Lösung von 9 g Mercaptoethanol in 50 g Wasser innerhalb von 2 Stunden und als Zulauf 2 eine Lösung von 7,5 g Azobis (2-methylbutyronitril) in 70 g Isopropanol innerhalb von 3 Stunden zudosiert. Anschließend wird das Reaktionsgemisch 1 Stunde bei einer Temperatur von 80°C gerührt, dann mit einer Lösung von 1,5 g Azobis (2-methylbutyronitril) in wenig Iso- propanol versetzt und das Reaktionsgemisch weitere 3 Stunden bei 80°C gerührt. Das Isopropanol wird anschließend mit Hilfe einer Wasserdampfdestillation aus dem Reaktionsgemisch entfernt. Man erhält eine gelbe und geruchsarme Polymerlösung mit einem Fest¬ stoffgehalt von 40 % und einer geringen Restmonomerenkonzentra- tion (80 ppm) . Das Homopolymerisat des Vinylimidazols hat einen K-Wert von 21,5 und ein Molekulargewicht von 23 000.In a polymerization apparatus, a mixture of 300 g of VI and 400 g of water is heated to a temperature of 80 ° C. in a nitrogen atmosphere with stirring. After this temperature has been reached, a solution of 9 g of mercaptoethanol in 50 g of water is metered in as feed 1 over the course of 2 hours and as feed 2 a solution of 7.5 g of azobis (2-methylbutyronitrile) in 70 g of isopropanol is metered in over the course of 3 hours. The reaction mixture is then stirred for 1 hour at a temperature of 80 ° C., then a solution of 1.5 g of azobis (2-methylbutyronitrile) in a little isopropanol is added and the reaction mixture is stirred for a further 3 hours at 80 ° C. The isopropanol is then removed from the reaction mixture using steam distillation. A yellow and low-odor polymer solution is obtained with a solids content of 40% and a low residual monomer concentration (80 ppm). The homopolymer of vinylimidazole has a K value of 21.5 and a molecular weight of 23,000.
Vergleichsbeispiele gemäß der DE-A-28 14 287Comparative examples according to DE-A-28 14 287
Vergleichsbeispiel 1Comparative Example 1
Gemäß den Angaben in Beispiel 6 der DE-A-28 14 287 wurde eine Mischung aus 9,4 g VI, 22,2 g VP und 120 g Methanol beim Siede¬ punkt des Reaktionsgemisches unter Durchleiten von Stickstoff in Gegenwart von 0,6 g Azoisobuttersäuredinitril als Initiator copolymerisiert. Man erhielt eine geruchsintensive Polymerlösung mit einem Feststoffgehalt von 24,6 %. Das Copolymerisat hatte eine K-Wert von 49. Die Polymerlösung enthielt 650 ppm VI und 6 600 ppm VP.According to the information in Example 6 of DE-A-28 14 287, a mixture of 9.4 g VI, 22.2 g VP and 120 g methanol was obtained at the boiling point of the reaction mixture while passing nitrogen through in the presence of 0.6 g Copolymerized azoisobutyronitrile as an initiator. An odor-intensive polymer solution with a solids content of 24.6% was obtained. The copolymer had a K value of 49. The polymer solution contained 650 ppm VI and 6 600 ppm VP.
Vergleichsbeispiel 2Comparative Example 2
Gemäß der in Beispiel 5 der DE-A-28 14 287 angegebenen Vorschrift wurde eine Mischung aus 18,8 g VI, 11,1 g VP und 120 g Methanol mit 6 g Azoisobuttersäuredinitril als Initiator beim Siedepunkt des Reaktionsgemisches copolymerisiert. Man erhielt eine ge¬ ruchsintensive Polymerlösung mit einem Feststoffgehalt von 22,3 %. Die Lösung enthielt 1,15 % nichtpolymerisiertes VI und 0,62 % nichtpolymerisiertes VP. Der K-Wert des Copolymerisats be- trug 42, 6. Vergleichsbeispiel 3According to the procedure given in Example 5 of DE-A-28 14 287, a mixture of 18.8 g VI, 11.1 g VP and 120 g methanol was copolymerized with 6 g azoisobutyronitrile as initiator at the boiling point of the reaction mixture. An odor-intensive polymer solution with a solids content of 22.3% was obtained. The solution contained 1.15% unpolymerized VI and 0.62% unpolymerized VP. The K value of the copolymer was 42.6. Comparative Example 3
In einem 500 ml fassenden Kolben wurden 78 g VI, 78 g Wasser und 2 g Azoisobuttersäuredinitril vorgelegt und unter Stickstoff- atmosphäre 6 Stunden bei 80°C gerührt. Man erhielt eine geruchs¬ intensive Polymerlösung mit einem Feststoffgehalt von 50,6 %. Der VI-Gehalt der Lösung betrug 0,42 %. Das Homopolymerisat von VI hatte einen K-Wert von 43,9.78 g of VI, 78 g of water and 2 g of azoisobutyronitrile were placed in a 500 ml flask and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere. An odor-intensive polymer solution with a solids content of 50.6% was obtained. The VI content of the solution was 0.42%. The homopolymer of VI had a K value of 43.9.
Wie die Vergleichsbeispiele belegen, erhält man gemäß den Bei¬ spielen der DE-A-28 14 287 keine niedrigmolekularen, restmonome- renarmen Polymerlösungen. As the comparative examples show, according to the examples in DE-A-28 14 287, no low-molecular, low-monomer polymer solutions are obtained.

Claims

Patentansprüche Claims
1. Homopolymerisate von 1 Vinylimidazol und Copolymerisate aus 1-Vinylimidazol und 1-vinylpyrrolidon, dadurch gekennzeich¬ net, daß sie jeweils Schwefel in gebundener Form enthalten und einen K-Wert von 10 bis 40 (bestimmt nach H. Fikentscher in 0,1 n wäßriger Kochsalzlösung bei 25°C und einer Polymer¬ konzentration von 1 Gew.-%) haben.1. Homopolymers of 1 vinylimidazole and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone, characterized in that they each contain sulfur in bound form and have a K value of 10 to 40 (determined according to H. Fikentscher in 0.1 n aqueous saline solution at 25 ° C. and a polymer concentration of 1% by weight).
2. Homo- und Copolymerisate nach Anspruch 1, dadurch gekenn¬ zeichnet, daß sie erhältlich sind durch radikalische Polyme¬ risation von 1-Vinylimidazol oder von Mischungen aus 1-Vinyl- imidazol und 1-Vinylpyrrolidon in C-.- bis C -Alkoholen, Wasser oder in Mischungen aus Wasser und mindestens einem C*.- bis C -Alkohol in Gegenwart von Polymerisationsreglern, die Schwefel in gebundener Form enthalten.2. Homopolymers and copolymers according to claim 1, characterized gekenn¬ characterized in that they are obtainable by radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C- . - to C -alcohols, water or in mixtures of water and at least one C * . - to C -alcohol in the presence of polymerization regulators which contain sulfur in bound form.
3. Verfahren zur Herstellung von Polymerisaten nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man 1-Vinylimidazol oder3. A process for the preparation of polymers according to claim 1 or 2, characterized in that 1-vinylimidazole or
Mischungen aus 1-Vinylimidazol und 1-Vinylpyrrolidon in Ci- bis C -Alkoholen, Wasser oder in Mischungen aus Wasser und mindestens einem C-.- bis C -Alkohol in Gegenwart von Polyme¬ risationsreglern, die Schwefel in gebundener Form enthalten, radikalisch polymerisiert .Mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in Ci to C alcohols, water or in mixtures of water and at least one C- . - Radically polymerized to C alcohol in the presence of polymerization regulators which contain sulfur in bound form.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man die Polymerisationsregler in Mengen von 0,1 bis 15 Gew.-%, bezogen auf die Monomeren, einsetzt.4. The method according to claim 3, characterized in that one uses the polymerization regulator in amounts of 0.1 to 15 wt .-%, based on the monomers.
5. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß man als Polymerisationsregler Mercaptoverbindungen, Dialkyl- sulfide, Dialkyldisulfide und/oder Diarylsulfide einsetzt.5. The method according to claim 3 or 4, characterized in that mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diarylsulfides are used as polymerization regulators.
6. Verfahren nach einem der Ansprüche 3 bis 5, dadurch gekenn¬ zeichnet, daß man die Polymerisationsregler während der Poly¬ merisation der Monomeren kontinuierlich oder portionsweise zugibt .6. The method according to any one of claims 3 to 5, characterized gekenn¬ characterized in that the polymerization regulator during the polymerisation of the monomers is added continuously or in portions.
7. Verwendung der Polymerisate nach Anspruch 1 oder 2 als Farb¬ stoffÜbertragungsinhibitor in Waschmitteln. Homo- und Copolymerisate von 1-Vinylimidazol, Verfahren zu ihrer Herstellung und ihre Verwendung7. Use of the polymers according to claim 1 or 2 as dye transfer inhibitor in detergents. Homopolymers and copolymers of 1-vinylimidazole, process for their preparation and their use
ZusammenfassungSummary
Homo- und Copolymerisate von 1-Vinylimidazol, Verfahren zur Her¬ stellung von niedrigmolekularen Homopolymerisaten des 1-Vinyl- imidazols und Copolymerisaten von 1-Vinylimidazol und 1-Vinyl- pyrrolidon durch radikalische Polymerisation von 1-Vinylimidazol oder von Mischungen aus 1-Vinylimidazol und 1-Vinylpyrrolidon in Cι_- bis C -Alkoholen, Wasser oder Mischungen aus Wasser und minde¬ stens einem C - bis C -Alkohol in Gegenwart von Polymerisations¬ reglern, die Schwefel in gebundener Form enthalten. Man erhält restmonomerarme, niedrigmolekulare Polymerlösungen und Verwendung der Polymerisate als Farbstoffübertragungsinhibitor in Waschmit¬ teln. Homopolymers and copolymers of 1-vinylimidazole, process for the preparation of low molecular weight homopolymers of 1-vinylimidazole and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone by radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C 1 to C alcohols, water or mixtures of water and at least one C 1 to C alcohol in the presence of polymerization regulators which contain sulfur in bound form. Low-monomer, low molecular weight polymer solutions are obtained and the polymers are used as dye transfer inhibitors in detergents.
EP94916182A 1993-05-13 1994-05-02 Homopolymers and copolymers of 1-vinylimidazole, method of producing them and their use Expired - Lifetime EP0698046B1 (en)

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